WO2021199840A1 - 脂肪族ポリエステル系生分解性樹脂用分解促進剤、生分解性樹脂組成物、および脂肪族ポリエステル系生分解性樹脂の分解促進方法 - Google Patents
脂肪族ポリエステル系生分解性樹脂用分解促進剤、生分解性樹脂組成物、および脂肪族ポリエステル系生分解性樹脂の分解促進方法 Download PDFInfo
- Publication number
- WO2021199840A1 WO2021199840A1 PCT/JP2021/007757 JP2021007757W WO2021199840A1 WO 2021199840 A1 WO2021199840 A1 WO 2021199840A1 JP 2021007757 W JP2021007757 W JP 2021007757W WO 2021199840 A1 WO2021199840 A1 WO 2021199840A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- magnesium sulfate
- aliphatic polyester
- basic magnesium
- biodegradable resin
- resin composition
- Prior art date
Links
- 229920006167 biodegradable resin Polymers 0.000 title claims abstract description 56
- 229920003232 aliphatic polyester Polymers 0.000 title claims abstract description 30
- 239000011342 resin composition Substances 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 10
- 230000015556 catabolic process Effects 0.000 title abstract 3
- 238000006731 degradation reaction Methods 0.000 title abstract 3
- 230000001737 promoting effect Effects 0.000 title description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 144
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 70
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 66
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 32
- 239000004630 polybutylene succinate adipate Substances 0.000 claims description 32
- -1 polybutylene succinate adipate Polymers 0.000 claims description 31
- 238000000354 decomposition reaction Methods 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 8
- 229920002961 polybutylene succinate Polymers 0.000 description 7
- 239000004631 polybutylene succinate Substances 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000013535 sea water Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920000704 biodegradable plastic Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000012773 agricultural material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000036284 oxygen consumption Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000206601 Carnobacterium mobile Species 0.000 description 1
- 208000030814 Eating disease Diseases 0.000 description 1
- 208000019454 Feeding and Eating disease Diseases 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014632 disordered eating Nutrition 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
- C08K2003/3063—Magnesium sulfate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention relates to a decomposition accelerator for an aliphatic polyester-based biodegradable resin, a biodegradable resin composition, and a method for promoting the decomposition of an aliphatic polyester-based biodegradable resin.
- a biodegradable resin composition having various properties enhanced while maintaining biodegradability has been proposed. For example, by blending wallastnite as an inorganic filler into an aliphatic polyester resin (polybutylene succinate-lactic acid copolymer), a resin composition with enhanced rigidity, heat resistance and impact resistance while maintaining biodegradability. The thing is disclosed (see, for example, Patent Document 1).
- Aliphatic polyester obtained by the polycondensation method from aliphatic dicarboxylic acid and glycol is known as a chemically synthesized biodegradable plastic.
- succinic acid-based biodegradable resins such as polybutylene succinate adipate (PBSA) have marine degradability, it is desired to further enhance marine degradability. Since this PBSA is soft, its rigidity is low, and its use is limited. There is a demand for a biodegradable resin composition which has better marine decomposability than the conventional one and can obtain a molded product having a high flexural modulus.
- an object of the present invention is to provide a method for promoting the decomposition of an aliphatic polyester-based biodegradable resin.
- the decomposition accelerator for an aliphatic polyester-based biodegradable resin according to the present invention contains basic magnesium sulfate.
- the biodegradable resin composition according to the present invention contains polybutylene succinate adipate and basic magnesium sulfate.
- the method for accelerating the decomposition of the aliphatic polyester-based biodegradable resin according to the present invention includes adding basic magnesium sulfate to the aliphatic polyester-based biodegradable resin and then kneading.
- a biodegradable resin composition capable of obtaining a decomposition accelerator for an aliphatic polyester-based biodegradable resin having a higher effect than before, an excellent marine degradability, and a molded product having a high bending elasticity.
- a method for promoting the decomposition of an aliphatic polyester-based biodegradable resin can be provided.
- basic magnesium sulfate has an action of promoting the decomposition of an aliphatic polyester-based biodegradable resin, particularly polybutylene succinate adipate (PBSA).
- PBSA polybutylene succinate adipate
- the resin composition obtained by blending polybutylene succinate adipate (PBSA) with basic magnesium sulfate is decomposed in seawater more than before.
- PBSA polybutylene succinate adipate
- a molded product having a high flexural modulus can be obtained.
- Basic magnesium sulfate is represented by MgSO 4 ⁇ 5Mg (OH) 2 ⁇ 3H 2 O, for example, sodium hydroxide, magnesium hydroxide, magnesium oxide, as raw materials and an alkaline substance and magnesium sulfate, such as calcium hydroxide, It can be obtained by hydrothermal synthesis.
- the basic magnesium sulfate either fibrous basic magnesium sulfate or fan-shaped basic magnesium sulfate may be used. Fibrous basic magnesium sulfate is preferable, but fibrous basic magnesium sulfate and fan-like basic magnesium sulfate can also be used in combination.
- the fibrous basic magnesium sulfate has an average fiber length generally in the range of 2 to 100 ⁇ m, preferably 5 to 50 ⁇ m, and an average fiber diameter of generally 0.1 to 2.0 ⁇ m, preferably 0.1 to 1.0 ⁇ m. The range.
- the fibrous basic magnesium sulfate generally has an average aspect ratio (average fiber length / average fiber diameter) of 2 or more, preferably 3 to 1000, more preferably 3 to 100, and particularly preferably 5 to 50.
- the average fiber length and average fiber diameter of fibrous basic magnesium sulfate can be calculated from the average number of each of the fiber length and fiber diameter measured by image analysis from a magnified image by a scanning electron microscope (SEM). can.
- the fan-shaped basic magnesium sulfate is a particle in which a part of a plurality of fibrous basic magnesium sulfate is joined and connected in a fan shape.
- the average particle length is 2 to 100 ⁇ m
- the average particle width is 1 to 40 ⁇ m
- the average aspect ratio is. It is about 1 to 100.
- the average particle length refers to the dimension in the longitudinal direction of the particle
- the average particle width refers to the maximum dimension in the lateral direction of the particle.
- the longitudinal direction of the particles is the direction in which the particle length is maximized
- the lateral direction of the particles is the direction orthogonal to the longitudinal direction.
- the average aspect ratio is a ratio (average particle length / average particle diameter).
- Each fibrous basic magnesium sulfate constituting the fan-shaped basic magnesium sulfate has an average fiber length of 2 to 100 ⁇ m, an average fiber diameter of 0.1 to 5 ⁇ m, and an average aspect ratio of 1 to 1000.
- the plurality of fibrous basic magnesium sulfates are bundled at one end and spread at the other end, for example. Further, the plurality of fibrous basic magnesium sulfates may be bundled at an arbitrary position in the longitudinal direction and have spreads at both ends.
- Such fan-shaped basic magnesium sulfate can be produced and confirmed according to the methods described in, for example, Japanese Patent Publication No. 4-36092 and Japanese Patent Publication No. 6-99147.
- the fan-shaped basic magnesium sulfate does not necessarily have to be in a state in which individual fibrous basic magnesium sulfates are confirmed, and in some cases, fibrous basic magnesium sulfates are bonded to each other in the longitudinal direction. May be good. If it is confirmed that the fibrous basic magnesium sulfate having the above-mentioned shape and further having an average fiber length, an average fiber diameter, and an average aspect ratio in a predetermined range is contained, the fan-shaped base used in the present invention is used. It can be regarded as magnesium sulfate.
- Wallastnite and the like are known as an inorganic filler blended in a biodegradable resin in order to improve physical characteristics. Since wallastonite is insoluble in seawater, it is released into the ocean as a decomposition residue of biodegradable resin. In this case, the accumulation of released wallastnite may cause unexpected problems.
- biodegradable resin to which the decomposition accelerator of the present invention is applied examples include an aliphatic polyester-based biodegradable resin which is a polycondensate of an aliphatic dicarboxylic acid and glycol.
- examples of the aliphatic dicarboxylic acid include succinic acid and adipic acid, and an aliphatic polyester-based biodegradable resin synthesized by polycondensation of these and glycol can be preferably used.
- succinic acid-based biodegradable resin examples include polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), and polybutylene succinate lactate (PBSL).
- PBS polybutylene succinate
- PBSA polybutylene succinate adipate
- PBSL polybutylene succinate lactate
- PBSLC polybutylene succinate hydrocaproate
- PBSC polybutylene succinate carbonate
- PBST polybutylene succinate terephthalate
- PBS-co-DEGS polybutylene succinate diethylene glycol succinate
- PBS-co-BDGA Polybutylene succinate butylene
- PBSF polybutylene succinate fluoride
- adipic acid-based biodegradable resin examples include polybutylene adipate (PBA), polybutylene adipate terephthalate (PBAT), and polyethylene adipate terephthalate (PEAT).
- PBA polybutylene adipate
- PBAT polybutylene adipate terephthalate
- PEAT polyethylene adipate terephthalate
- One type of these biodegradable resins may be used alone, or a plurality of them may be used.
- the decomposition accelerator of the present invention containing basic magnesium sulfate is particularly effective in promoting the decomposition of PBSA.
- the basic magnesium sulfate is preferably present in a proportion of 1 to 70% of the total mass of the aliphatic polyester-based biodegradable resin and the basic magnesium sulfate, more preferably 1 to 50%.
- Other components may be present as long as they do not interfere with the decomposition of the aliphatic polyester-based biodegradable resin.
- PBSA Polybutylene succinate adipate
- the biodegradable resin composition of the present invention contains polybutylene succinate adipate (PBSA).
- PBSA polybutylene succinate adipate
- PBSA polybutylene succinate adipate
- PBSA is particularly excellent in marine decomposability and resin physical characteristics, and can be synthesized by a polycondensation method using, for example, 1,4-butanediol, succinic acid and adipic acid. ..
- PBSA and basic magnesium sulfate are first mixed.
- a tumbler, a blender, a Henschel mixer or the like can be used for mixing.
- the content of basic magnesium sulfate in the biodegradable resin composition is preferably 1 to 70%, preferably 1 to 50%, assuming that the total mass of PBSA and basic magnesium sulfate is 100. More preferable.
- the biodegradable resin composition of the present invention can be obtained by melt-kneading the obtained mixture at 160 to 210 ° C. using a twin-screw kneader or the like. Since the biodegradable resin composition of the present invention contains basic magnesium sulfate, it has higher marine degradability than before. Moreover, by using the biodegradable resin composition of the present invention, it is possible to produce a molded product having a high flexural modulus.
- the biodegradable resin composition of the present invention may contain other components as long as the effects of the present invention are not impaired.
- a rolling molding machine (calendar molding machine or the like), a vacuum molding machine, an extrusion molding machine, an injection molding machine, a blow molding machine, a press molding machine or the like can be used.
- the molded product of the present invention is a soft biodegradable plastic.
- Soft biodegradable plastics can be used in film / sheet products for packaging materials such as agricultural multi-films and garbage bags.
- the molded product of the present invention is suitably used in a wide range of applications such as packaging materials for packaging various foods, chemicals, miscellaneous goods and other liquids, powders and solids, agricultural materials, and building materials.
- Specific applications include, for example, injection molded products (for example, fresh food trays, coffee capsules, fast food containers, outdoor leisure products, etc.), extruded products (films, for example, fishing threads, fishing nets, vegetation nets, water retention sheets, etc.). Etc.), hollow molded products (bottles, etc.) and the like.
- information and electronic materials such as toner binders and ink binders for thermal transfer, automobile interior parts such as electrical product housings, instrument panels, seats and pillars, and automobile exterior structural materials such as bumpers, front grilles and wheel covers. It can also be used for parts and the like.
- packaging materials such as packaging films, bags, trays, capsules, bottles, cushioning foams, fish boxes and the like, and agricultural materials. Examples of agricultural materials include mulching films, tunnel films, house films, sunshades, weed-proof sheets, ridge sheets, germination sheets, vegetation mats, nursery beds, flower pots and the like.
- the biodegradable resin composition of the present invention has excellent marine decomposability, and the flexural modulus can be adjusted by the content of basic magnesium sulfate, so that molded bodies for various purposes can be obtained. ..
- ⁇ Basic magnesium sulfate> A-1 Fibrous basic magnesium sulfate Mosheidi A-1, manufactured by Ube Material Industries Ltd., average major axis 15 ⁇ m, average minor axis 0.5 ⁇ m, average aspect ratio 30
- A-2 Fan-shaped basic magnesium sulfate, average particle length 33.0 ⁇ m, average particle width 6.0 ⁇ m, average aspect ratio 5.5
- PBSA Polybutylene succinate adipate
- B Polybutylene succinate adipate (BioPBS FD92PM, manufactured by PTT MCC Biochem)
- ⁇ Inorganic filler> C Wallast Night
- Example 2 The resin of Example 2 in the same manner as in Example 1 except that the fibrous basic magnesium sulfate (A-1) was changed to 10 parts by mass and the polybutylene succinate adipate (B) was changed to 90 parts by mass. The composition was obtained.
- Example 3 The resin of Example 3 in the same manner as in Example 1 except that the fibrous basic magnesium sulfate (A-1) was changed to 30 parts by mass and the polybutylene succinate adipate (B) was changed to 70 parts by mass. The composition was obtained.
- Example 4 The resin of Example 4 in the same manner as in Example 1 except that the fibrous basic magnesium sulfate (A-1) was changed to 50 parts by mass and the polybutylene succinate adipate (B) was changed to 50 parts by mass. The composition was obtained.
- Example 5 The resin composition of Example 5 was obtained in the same manner as in Example 1 except that the fibrous basic magnesium sulfate (A-1) was changed to the same amount of fan-shaped basic magnesium sulfate (A-2).
- Example 6 The resin composition of Example 6 was obtained in the same manner as in Example 2 except that the fibrous basic magnesium sulfate (A-1) was changed to the same amount of fan-shaped basic magnesium sulfate (A-2).
- Example 7 The resin composition of Example 7 was obtained in the same manner as in Example 3 except that the fibrous basic magnesium sulfate (A-1) was changed to the same amount of fan-shaped basic magnesium sulfate (A-2).
- Comparative example 2 A resin composition of Comparative Example 2 was obtained in the same manner as in Example 3 except that the fibrous basic magnesium sulfate (A-1) was changed to the same amount of wallastonite (C).
- Table 1 summarizes the compounding compositions of the resin compositions of Examples and Comparative Examples.
- Each resin composition is molded using a small injection molding machine (C. Mobile 0813, manufactured by Shinko Selvik Co., Ltd.) to obtain a strip test piece (length 50 mm, width 5 mm, thickness 2 mm) for evaluation of mechanical properties. rice field.
- C. Mobile 0813 manufactured by Shinko Selvik Co., Ltd.
- Example 3 and Comparative Example 1 The compacts obtained in Example 3 and Comparative Example 1 were pulverized by freezing and pulverization to prepare a powder sample.
- the total oxygen consumption (TOD) of the test sample was 95.4 mgO 2 .
- the oxygen consumption after 30 days (BOD (biochemical oxygen demand) was measured, and the degree of biodegradation (%) was calculated by ((BOD) / (TOD) ⁇ 100).
- Table 2 below shows the flexural modulus of the molded product using each resin composition.
- Comparative Example 2 even when an inorganic filler such as wallastonite is blended, the flexural modulus can be increased as compared with the case where it is not blended (Comparative Example 1). However, wallastonite is inferior in biodegradation and does not decompose in the ocean.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
以下、本発明の実施形態を詳細に説明する。
塩基性硫酸マグネシウムは、MgSO4・5Mg(OH)2・3H2Oで表され、例えば、水酸化ナトリウム、水酸化マグネシウム、酸化マグネシウム、水酸化カルシウムなどのアルカリ性物質と硫酸マグネシウムとを原料として、水熱合成により得ることができる。塩基性硫酸マグネシウムとしては、繊維状塩基性硫酸マグネシウムおよび扇状塩基性硫酸マグネシウムのいずれを用いてもよい。繊維状塩基性硫酸マグネシウムが好ましいが、繊維状塩基性硫酸マグネシウムと扇状塩基性硫酸マグネシウムとを併用することもできる。
本発明の分解促進剤が適用される生分解性樹脂としては、脂肪族ジカルボン酸とグリコールとの重縮合物である脂肪族ポリエステル系生分解性樹脂が挙げられる。脂肪族ジカルボン酸としては、コハク酸やアジピン酸が挙げられ、これらとグリコールとの重縮合によって合成される脂肪族ポリエステル系生分解性樹脂が好適に用いることができる。
これらの生分解性樹脂は、1種類を単独で用いても良いし、複数を用いても良い。塩基性硫酸マグネシウムを含む本発明の分解促進剤は、上述した生分解性樹脂のなかでも、特にPBSAの分解促進に効果を発揮する。
本発明の生分解性樹脂組成物には、ポリブチレンサクシネート・アジペート(PBSA)が含有される。ポリブチレンサクシネート・アジペート(PBSA)は、海洋分解性および樹脂物性等が特に優れており、例えば1,4-ブタンジオール、コハク酸およびアジピン酸を用いて、重縮合法により合成することができる。
本発明の生分解性樹脂組成物の製造に当たっては、まず、PBSAと塩基性硫酸マグネシウムとを混合する。混合には、タンブラー、ブレンダー、ヘンシェルミキサー等を用いることができる。生分解性樹脂組成物における塩基性硫酸マグネシウムの含有量は、PBSAと塩基性硫酸マグネシウムとの合計質量を100とした場合、1~70%であることが好ましく、1~50%であることがより好ましい。
本発明の生分解性樹脂組成物を成形することによって、種々の成形体を製造することができる。樹脂組成物の成形には、例えば圧延成形機(カレンダー成形機など)、真空成形機、押出成形機、射出成形機、ブロー成形機、プレス成形機などを用いることができる。
<塩基性硫酸マグネシウム>
A-1 :繊維状塩基性硫酸マグネシウム モスハイジA-1、宇部マテリアルズ(株)製、平均長径15μm、平均短径0.5μm、平均アスペクト比30
A-2 :扇状塩基性硫酸マグネシウム、平均粒子長33.0μm、平均粒子幅6.0μm、平均アスペクト比5.5
<ポリブチレンサクシネート・アジペート(PBSA)>
B :ポリブチレンサクシネート・アジペート(BioPBS FD92PM、PTT MCCBiochem製)
<無機充填剤>
C :ワラストナイト
繊維状塩基性硫酸マグネシウム(A-1)5質量部、ポリブチレンサクシネート・アジペート(B)95部を混合した。得られた混合物を、二軸溶融混練押出機(L/D=25、(株)井元製作所製)を用いて160℃で溶融混練して、実施例1の樹脂組成物を得た。
繊維状塩基性硫酸マグネシウム(A-1)を10質量部に変更し、ポリブチレンサクシネート・アジペート(B)を90質量部に変更した以外は実施例1と同様にして、実施例2の樹脂組成物を得た。
繊維状塩基性硫酸マグネシウム(A-1)を30質量部に変更し、ポリブチレンサクシネート・アジペート(B)を70質量部に変更した以外は実施例1と同様にして、実施例3の樹脂組成物を得た。
繊維状塩基性硫酸マグネシウム(A-1)を50質量部に変更し、ポリブチレンサクシネート・アジペート(B)を50質量部に変更した以外は実施例1と同様にして、実施例4の樹脂組成物を得た。
繊維状塩基性硫酸マグネシウム(A-1)を同量の扇状塩基性硫酸マグネシウム(A-2)に変更した以外は実施例1と同様にして、実施例5の樹脂組成物を得た。
繊維状塩基性硫酸マグネシウム(A-1)を同量の扇状塩基性硫酸マグネシウム(A-2)に変更した以外は実施例2と同様にして、実施例6の樹脂組成物を得た。
繊維状塩基性硫酸マグネシウム(A-1)を同量の扇状塩基性硫酸マグネシウム(A-2)に変更した以外は実施例3と同様にして、実施例7の樹脂組成物を得た。
塩基性硫酸マグネシウム(A)を配合せず、ポリブチレンサクシネート・アジペート(B)単味を比較例1とした。
繊維状塩基性硫酸マグネシウム(A-1)を同量のワラストナイト(C)に変更した以外は実施例3と同様にして、比較例2の樹脂組成物を得た。
小型射出成形機(C.Mobile0813、(株)新興セルビック製)を用いて各樹脂組成物を成形して、力学物性評価用の短冊試験片(長さ50mm、幅5mm、厚さ2mm)を得た。
万能力学試験機((株)イマダ製)を用いて、JISK7171に準拠した方法で3点曲げ試験を行った。支点間距離は40mm、負荷速度は10mm/minとした。得られた荷重たわみ曲線から、曲げ弾性率を評価した。
実施例3、比較例1で得られた成形体を冷凍粉砕により粉砕して、粉末試料を調製した。粉末試料(実施例3は76mg、比較例1は53mg)と200mLの天然海水(福岡県福岡市で採取)を密閉容器に収容し、30℃恒温槽中にて撹拌した。被験試料の全酸素消費量(TOD)は、95.4mgO2とした。30日後の酸素消費量(BOD(生物化学的酸素要求量)を測定し、((BOD)/(TOD)×100)によって生分解度(%)を算出した。
また、塩基性硫酸マグネシウムが配合されることによって、海洋分解性は著しく向上している。
Claims (8)
- 塩基性硫酸マグネシウムを含む脂肪族ポリエステル系生分解性樹脂用分解促進剤。
- 前記脂肪族ポリエステル系生分解性樹脂が、脂肪族ジカルボン酸とグリコールとの重縮合物である請求項1記載の脂肪族ポリエステル系生分解性樹脂用分解促進剤。
- 前記脂肪族ポリエステル系生分解性樹脂は、ポリブチレンサクシネート・アジペートである請求項2記載の脂肪族ポリエステル系生分解性樹脂用分解促進剤。
- 前記塩基性硫酸マグネシウムは、少なくとも一部が繊維状塩基性硫酸マグネシウムである請求項1乃至3のいずれか1項記載の脂肪族ポリエステル系生分解性樹脂用分解促進剤。
- 前記塩基性硫酸マグネシウムは、少なくとも一部が扇状塩基性硫酸マグネシウムである請求項1乃至3のいずれか1項記載の脂肪族ポリエステル系生分解性樹脂用分解促進剤。
- ポリブチレンサクシネート・アジペートと、塩基性硫酸マグネシウムとを含有する生分解性樹脂組成物。
- 前記ポリブチレンサクシネート・アジペートと前記塩基性硫酸マグネシウムとの合計質量を100とした場合、前記塩基性硫酸マグネシウムの含有量は、1~70%である請求項6記載の生分解性樹脂組成物。
- 脂肪族ポリエステル系生分解性樹脂に塩基性硫酸マグネシウムを添加し、次いで混練することを含む脂肪族ポリエステル系生分解性樹脂の分解促進方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020227032670A KR20220143922A (ko) | 2020-03-30 | 2021-03-01 | 지방족 폴리에스테르계 생분해성 수지용 분해 촉진제, 생분해성 수지 조성물, 및 지방족 폴리에스테르계 생분해성 수지의 분해 촉진 방법 |
DE112021002123.0T DE112021002123T5 (de) | 2020-03-30 | 2021-03-01 | Abbaupromotoren für biologisch abbaubares aliphatisches Polyesterharz, biologisch abbaubare Harzzusammensetzung und Verfahren zum Beschleunigen des Abbaus von biologisch abbaubarem aliphatischem Polyesterharz |
CN202180023205.XA CN115315473B (zh) | 2020-03-30 | 2021-03-01 | 生物可分解性树脂组成物及树脂的分解促进方法 |
US17/913,287 US20230167267A1 (en) | 2020-03-30 | 2021-03-01 | Degradation promoter for aliphatic polyester biodegradable resin, biodegradable resin composition, and method for promoting degradation of aliphatic polyester biodegradable resin |
JP2022511678A JP7382490B2 (ja) | 2020-03-30 | 2021-03-01 | 脂肪族ポリエステル系生分解性樹脂用分解促進剤、生分解性樹脂組成物、および脂肪族ポリエステル系生分解性樹脂の分解促進方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020-059410 | 2020-03-30 | ||
JP2020059410 | 2020-03-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021199840A1 true WO2021199840A1 (ja) | 2021-10-07 |
Family
ID=77930305
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/007757 WO2021199840A1 (ja) | 2020-03-30 | 2021-03-01 | 脂肪族ポリエステル系生分解性樹脂用分解促進剤、生分解性樹脂組成物、および脂肪族ポリエステル系生分解性樹脂の分解促進方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230167267A1 (ja) |
JP (1) | JP7382490B2 (ja) |
KR (1) | KR20220143922A (ja) |
CN (1) | CN115315473B (ja) |
DE (1) | DE112021002123T5 (ja) |
TW (1) | TWI830009B (ja) |
WO (1) | WO2021199840A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023145665A1 (ja) * | 2022-01-25 | 2023-08-03 | 宇部マテリアルズ株式会社 | 生分解性樹脂組成物、成形体、および生分解樹脂組成物の製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04122438A (ja) * | 1990-09-14 | 1992-04-22 | Nippon Chem Ind Co Ltd | 空気浄化剤およびその製造方法 |
JPH06200280A (ja) * | 1992-09-25 | 1994-07-19 | Oiles Ind Co Ltd | 複層摺動部材 |
JP2005307128A (ja) * | 2004-04-26 | 2005-11-04 | Mitsui Chemicals Inc | ポリ乳酸系樹脂組成物 |
JP2010155392A (ja) * | 2008-12-26 | 2010-07-15 | Mitsubishi Chemicals Corp | 生分解性樹脂積層体及びその製造方法 |
JP2010270309A (ja) * | 2009-04-24 | 2010-12-02 | Sumitomo Chemical Co Ltd | 樹脂組成物の製造方法及び成形体 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61256920A (ja) | 1985-05-07 | 1986-11-14 | Ube Ind Ltd | 扇状マグネシウムオキシサルフエ−トおよびその製法 |
JP4609268B2 (ja) | 2005-09-30 | 2011-01-12 | 三菱化学株式会社 | 脂肪族ポリエステル樹脂組成物 |
JP2009013362A (ja) | 2007-07-09 | 2009-01-22 | Mitsubishi Chemicals Corp | 生分解性樹脂組成物及びその成型品 |
TWI525046B (zh) * | 2011-03-02 | 2016-03-11 | 宇部材料股份有限公司 | Fibrous alkaline magnesium sulfate powder and method for producing the same |
CN106008931B (zh) | 2016-06-08 | 2017-09-19 | 青岛科技大学 | 一种pbs/碱式硫酸镁晶须复合材料及制备方法 |
JPWO2018193893A1 (ja) * | 2017-04-17 | 2020-02-27 | 宇部マテリアルズ株式会社 | ポリオレフィン樹脂組成物及びポリオレフィン樹脂組成物成形体 |
WO2020138222A1 (ja) * | 2018-12-27 | 2020-07-02 | 宇部マテリアルズ株式会社 | ポリカーボネート樹脂組成物及びその製造方法、マスターバッチペレット、並びに成形体 |
KR20210141580A (ko) * | 2019-03-18 | 2021-11-23 | 우베 마테리알즈 가부시키가이샤 | 폴리카보네이트 수지 조성물 및 그 제조 방법, 마스터배치 펠릿, 및 성형체 |
-
2021
- 2021-03-01 WO PCT/JP2021/007757 patent/WO2021199840A1/ja active Application Filing
- 2021-03-01 CN CN202180023205.XA patent/CN115315473B/zh active Active
- 2021-03-01 JP JP2022511678A patent/JP7382490B2/ja active Active
- 2021-03-01 DE DE112021002123.0T patent/DE112021002123T5/de active Pending
- 2021-03-01 KR KR1020227032670A patent/KR20220143922A/ko unknown
- 2021-03-01 US US17/913,287 patent/US20230167267A1/en active Pending
- 2021-03-12 TW TW110108837A patent/TWI830009B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04122438A (ja) * | 1990-09-14 | 1992-04-22 | Nippon Chem Ind Co Ltd | 空気浄化剤およびその製造方法 |
JPH06200280A (ja) * | 1992-09-25 | 1994-07-19 | Oiles Ind Co Ltd | 複層摺動部材 |
JP2005307128A (ja) * | 2004-04-26 | 2005-11-04 | Mitsui Chemicals Inc | ポリ乳酸系樹脂組成物 |
JP2010155392A (ja) * | 2008-12-26 | 2010-07-15 | Mitsubishi Chemicals Corp | 生分解性樹脂積層体及びその製造方法 |
JP2010270309A (ja) * | 2009-04-24 | 2010-12-02 | Sumitomo Chemical Co Ltd | 樹脂組成物の製造方法及び成形体 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023145665A1 (ja) * | 2022-01-25 | 2023-08-03 | 宇部マテリアルズ株式会社 | 生分解性樹脂組成物、成形体、および生分解樹脂組成物の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2021199840A1 (ja) | 2021-10-07 |
US20230167267A1 (en) | 2023-06-01 |
TWI830009B (zh) | 2024-01-21 |
TW202204502A (zh) | 2022-02-01 |
JP7382490B2 (ja) | 2023-11-16 |
KR20220143922A (ko) | 2022-10-25 |
CN115315473A (zh) | 2022-11-08 |
CN115315473B (zh) | 2023-12-22 |
DE112021002123T5 (de) | 2023-01-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108102318B (zh) | 可生物分解的薄膜材料 | |
ES2333382T3 (es) | Nueva composicion polimerica biodegradable util para la preparacion de plastico biodegradable y proceso para la preparacion de dicha composicion. | |
Tang et al. | Recent advances in biopolymers and biopolymer-based nanocomposites for food packaging materials | |
US7619025B2 (en) | Biodegradable polymeric nanocomposite compositions particularly for packaging | |
KR101802362B1 (ko) | 무기항균제를 함유한 항균성 폴리락트산계 압출발포시트 및 그를 이용한 생분해성 항균 발포 성형품 | |
JP7139351B2 (ja) | 生分解性フィルム | |
CN113597442A (zh) | 生物降解性树脂组合物的制造方法 | |
JP7110228B2 (ja) | 生分解性フィルム | |
JP7382490B2 (ja) | 脂肪族ポリエステル系生分解性樹脂用分解促進剤、生分解性樹脂組成物、および脂肪族ポリエステル系生分解性樹脂の分解促進方法 | |
ES2673023T5 (es) | Plástico biodigestible, biocompostable y biodegradable | |
US20100076099A1 (en) | Biodegradable polymeric nanocomposite compositions particularly for packaging | |
Ghosh et al. | Green composites based on aliphatic and aromatic polyester: opportunities and application | |
JP7421635B2 (ja) | 生分解性樹脂組成物 | |
JP7240775B1 (ja) | 樹脂組成物及び成形品 | |
Jiménez et al. | Nano-biocomposites for food packaging | |
Nasrollahzadeh et al. | Application of biopolymers in bioplastics | |
Ibrahim et al. | Overview of Bioplastic Introduction and Its Applications in Product Packaging. Coatings 2021, 11, 1423 | |
WO2023145665A1 (ja) | 生分解性樹脂組成物、成形体、および生分解樹脂組成物の製造方法 | |
Ameer Ali et al. | Polylactic acid-based nanocomposites: an important class of biodegradable composites | |
KR20230078010A (ko) | 곡물이 함유된 생분해성 조성물 및 이를 이용한 가공품 제조방법 | |
JP4476469B2 (ja) | 生分解性フィルム | |
TR2023007733T2 (tr) | İnorgani̇k katki i̇çeren poli̇meri̇k terki̇pler ve bunlarin üreti̇m yöntemi̇ | |
WO2024024361A1 (ja) | 生分解性樹脂用可塑剤、それを含む樹脂組成物及び成形品 | |
JP2001031134A (ja) | 生分解性フィルム及びこれを用いた生分解性袋 | |
JP4132955B2 (ja) | 微生物崩壊性樹脂組成物および成形品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21781473 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2022511678 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20227032670 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21781473 Country of ref document: EP Kind code of ref document: A1 |